Manganese carbonyls, photolysis with

The formation of both Mn(CO)s and the CO-loss product, Mn2(CO)9, from UV photolysis of Mn2(CO)io has been investigated by ultrafast IR spectroscopy.Density functional calculations have been performed on the ground and excited states of MnCl(CO)5, as an aid to understanding the photochemistry of MX(C0)5 complexes (M = Mn, Re X = Cl, Br, I). The lowest energy excitations are to the Mn-Cl a orbital, and these states are dissociative for both axial and equatorial CO loss, but not for Mn-Cl bond homolysis. The photochemistry of manganese carbonyl complexes (58, R = Me, benzyl R = /-Pr, p-tolyl) depends critically on the R group.CO is released with R = Me, but with R = benzyl there is efficient homolysis of the Mn-R bond. ... 

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